FI100658B - Hair dyes - Google Patents

Abstract

PCT No. PCT/EP89/00834 Sec. 371 Date Jan. 25, 1991 Sec. 102(e) Date Jan. 25, 1991 PCT Filed Jul. 17, 1989 PCT Pub. No. WO90/01050 PCT Pub. Date Feb. 8, 1990.The invention relates to the use of compounds corresponding to formula (I) <IMAGE> (1) in which one of the substituents R1 or R2 is a nitro group while the other is hydrogen, halogen, an amino group, a mono- or dialkylamino group containing C1-4 alkyl groups, a C1-4 alkyl or alkoxy group, R3 and R4 independently of one another represent hydrogen or a C1-4 alkyl group, A is a >CHR6- or a >C=O- group, where R6 is hydrogen or a C1-4 alkyl group, and R5 is hydrogen or a C1-4 alkyl group, or salts thereof as substantive dyes in hair-dyeing compositions. When the substituent groups in formula I represent one of the combinations I-IV shown in the table below, the compounds are novel and are useful in hair-dyeing compositions. -R1 R2 R3 R4 R5 A -I: H NO2 H CH3 H CH2 -II: H NO2 CH3 CH3 H CH2 -III: NH2 NO2 H H H CH2 -IV: H NO2 H H CH3 CH2. -

Description

100658

Hair dye substances Härfärgningsmedel

The invention relates to hair dyes which contain direct colorants useful in the hair.

In addition to oxidative dyes, which are formed when one or more developer components are oxidatively coupled to each other or to one or more component dyes, direct dyes, which are particularly useful in hair, play an important role in hair coloring. The advantage of direct dyes is that they can be used without oxidants. Compounds belonging to the group of nitrobenzene derivatives are mainly used as direct dyes. They are used either alone or in combination with other direct dyes such as anthraquinone dyes, indo-phenols, triphenylmethane dyes, cationic azo dyes or oxidative dyes.

Usually, hair dyes contain such direct hair dyes useful in the cosmetic carrier. Ointments, emulsions, gels, shampoos, foam aerosols or other preparations which can be used on the hair can be used as cosmetic carriers for direct dyes which can be used in the hair and any oxidative dye precursors which the hair dye may additionally contain in order to achieve certain color shades.

Good hair dyes must produce the desired color tones with sufficient intensity. In addition, they must be well absorbed into human hair, but without dyeing the scalp too strongly. The color obtained in this way must be highly resistant to light, heat, sweat, hair detergents and the chemicals used in the permanent treatment of the hair. Finally, they must be toxicologically and dermatologically safe.

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In addition, direct dyes must be well compatible with other dyes, for example oxidative dye precursors, and common components in oxidative dyes for hair, as direct dyes and oxidative dyes are preferably combined to modify color tones. For this reason, they must be highly resistant to reducing agents and oxygen-free.

Of the direct dyeing nitrobenzene derivatives, nitroanilines and their derivatives are particularly important because some of these dyes produce strong, highly light-resistant dyes. However, the disadvantages of the known direct coloring nitroaniline dyes are, on the one hand, their limited water solubility, which causes problems in the manufacture of hair dyes, and, on the other hand, their unsatisfactory washing resistance, i.e. that the hair color deteriorates after numerous washes. In addition, when direct color agents are used, it is difficult to obtain certain fashion colors, especially red shades. So far, 2-nitro-p-phenylenediamine and its amino-substituted derivatives have been commonly used for this purpose. However, most of these compounds are insufficiently soluble or dispersed in water. This often results in uneven vibrating results. Particularly in the case of colorants which contain high concentrations of dyes to produce certain shades, but also in the case of preparations which contain only a small amount of Liu-flowing carrier components, there is still a risk that the coloration will be weaker than expected because the dyes crystallize and remain in the dye bath instead. would be absorbed into the hair.

Surprisingly, it was found that these disadvantages are not related to certain 1, 2, 3, 4-tetrahydro-nitroquinoxalines, which therefore meet the requirements for direct dyes for use in the hair very well.

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The invention therefore relates to hair dyes containing straight dyes, which are characterized in that they contain as direct dyes one or more compounds of the formula (I) R1 R3 ΌγΝ'ί, R * wherein one of the groups R1 or Ra is a nitro group, while the other of them is hydrogen, halogen, an amino group, a mono- or dialkylamino group having 1 to 4 carbon atoms in the alkyl groups, an alkyl or alkoxy group having 1 to 4 carbon atoms in each case, R * and R * independently of one another denote hydrogen or an alkyl group having 1 to 4 carbon atoms a group, A is a> CHRe or> C ** O group, the symbol R6 denotes hydrogen or an alkyl group having 1 to 4 carbon atoms, and R5 represents hydrogen or an alkyl group having 1 to 4 carbon atoms, or a salt thereof.

Particularly suitable dyes are 1,2,3,4-tetrahydro-5-nitroquinoxaline and 1,2,3,4-tetrahydro-6-nitroquinoxaline.

The dyes according to the invention are generally obtained from the correspondingly substituted quinoxalines by customary synthetic methods. Thus, the preparation of 1,2,3,4-tetrahydro-5-nitroquinoxaline and 1,2,3,4-tetrahydro-6-nitroquinoxaline is described in J. Het. Chem. , 10, 213 (1973) as a reaction between the corresponding quinoxalines and sodium borohydride in methanol solution. However, the compounds of formula (I) are also obtained in other ways. Thus, J. Chem. Soc. , (1961), 5283, according to which 1,2,3,4-tetrahydro-7-nitro-2-oxoquinoxaline is obtained by reacting N- (2,4-dinitrophenyl) glycine with a mixture of sodium bicarbonate and sodium sulfide. in methanolic solution.

However, there is no mention in those publications that these compounds could be used to color hair.

The invention furthermore relates to novel compounds of the formula (I) as defined in claim 1, which are characterized by the following substituent combinations (I) to (IV):

R1 R2 R3 R4 R = A

I: H NOa H CHs H CHa II: H NOa CHa CHa H CHa III: NHa NOa H H H CHa IV: H NOa H H CHa CHa.

These compounds are likewise obtained in principle from similarly substituted quinoxalines; synthetic instructions are given in the examples.

The dyes of the general formula (I) produce very strong color shades in the hair, between yellow and red-orange, which are very resistant to light and washing. In addition, they are more soluble in aqueous temporal solutions than known nitroaniline dyes. Said compounds are dermatologically and toxicologically harmless and can therefore be used particularly well in hair dyes.

The dyes according to the invention can be used as such or also as their water-soluble salts. In this context, salts are considered to be water-soluble if they are soluble in water or aqueous mixtures in sufficiently large amounts for the purpose of coloring the hair.

Suitable water-soluble salts are, in particular, salts of strong bases, such as alkali metal salts, for example sodium or potassium salt or ammonium salts, and alkanolammonium salts having 2 to 4 carbon atoms in the time group, such as monoethanolammonium salt, triethanolammonium ammonium salt or isopropanol.

The hair dyes according to the invention may contain the direct coloring compounds of the formula (I) alone or in combination with known direct coloring agents, such as, for example, other nitrobenzene derivatives, anthraquinone dyes, triphenylmethane or azo dyes. In addition, since the direct dyes of formula (I) are highly resistant to reducing agents and oxidizing agents, they can also be used very well in combination with oxidizing dye precursors, i.e. for modifying the color tones obtained with oxidative dyes used in hair. Oxidation dyes used in the hair contain, as dye precursors, developer components that form oxidative dyes upon coupling by oxidation to each other or to suitable component dyes. Examples of developing agents which are used are primary aromatic amines in which the para or ortho position also has a free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2, 4,5,6-tetraaminopyrimide derivatives. As component colors, m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols are used.

For the preparation of the hair dyes according to the invention, the direct colorants used in the hair and possible oxidative dye precursors are incorporated into a suitable cosmetic carrier, for example creams, emulsions, gels or also surfactant-containing foaming solutions, for example shampoos,

Common components of these cosmetic preparations include, for example, wetting and emulsifying agents such as anionic, nonionic or ampholytic surfactants, for example 6,100,658 fatty alcohol sulphates, alkane sulphonates, alpha-olefin sulphonates, fatty alcohol polyglycol ether ethers, sulphate ether ethylene sulphates, with fatty acids and alkylphenols, sorbitan fatty acid esters and partial glycerides of fatty acids, fatty acid alkanolamides and thickeners such as methyl or hydroxyethylcellulose, starch, fatty alcohols, polymers, and cholesterol. The components of the cosmetic carrier are used for the preparation of the hair dyes according to the invention in ordinary amounts for this purpose; for example, emulsifiers are used in concentrations ranging from 0.5 to 30% by weight and thickeners are used in concentrations ranging from 0.1 to 25% by weight, based on the total weight of the colorant.

The hair dyes according to the invention contain straight dyes of the general formula I for use in the hair in an amount of 0.01 to 5.0% by weight, preferably 0.1 to 2% by weight, based on the total weight of the hair dye. In addition, oxidative dye precursors (developers and component dyes) used in the hair may be present in an amount of 0.01 to 5% by weight, preferably 1 to 3% by weight.

If the hair dye according to the invention contains oxidation-dye precursors, it is also advisable to add a small amount of a reducing agent, for example 0.5-2.0% by weight of sodium sulfite, to stabilize the oxidation dye precursors. In this case, before using the hair dye, an oxidant is added to the oxygen of the oxidant dye precursors--. development. In particular, hydrogen peroxide or an adduct between it and urea, melamine or sodium borate, as well as mixtures containing such hydrogen peroxide adducts and potassium peroxide sulfate, can be used as the oxidant.

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The hair dyes according to the invention can be used, regardless of the type of cosmetic preparation, for example as a cream, gel or shampoo, in a weakly acidic, neutral or alkaline environment. This hair dye is preferably used in the pH range of 6-10. Operating temperatures can range from 15 to 40 ° C. After an exposure time of 30 minutes, the hair dye is removed by rinsing the hair to be dyed. The hair is then washed with a mild shampoo and dried. Post-washing the hair with shampoo is unnecessary if a carrier rich in tensides, for example colored shampoo, was used.

The hair dyes according to the invention provide very strong hair dyes which have good durability properties, in particular also washing resistance, and which are very permanent in view of the deterioration and color changes caused by shampooing. The following examples illustrate the invention without limiting it.

eXAMPLES

Preparation Examples 1) 1,2,3,4-Tetrahydro-2-methyl-6-nitroquinoxaline 1 g of 2-methyl-6-nitroquinoxaline prepared according to Coll. Czech. Chem. Comm. , 30, 3106 (1965) from 4-nitro-1,2-diaminobenzene by reaction with methylglyoxal was dissolved in 30 ml of acetic acid. To this solution was added small amounts of sodium borohydride in small portions at + 5 ° C until the starting compound could no longer be detected from the solution by thin layer chromatography. The solution was then diluted with 200 ml of water and extracted twice with chloroform. The organic phase was washed with water and dried. After evaporation to dryness, the residue was dissolved in acetone and mixed with hydrochloric acid. The yield was 0.6 g (58% of theory). The 1,2,3,4-tetrahydro-2-methyl-6-nitroquinoxaline thus obtained had a melting point of 178 ° C.

2) 1,2,3,4-Tetrahydro-5-amino-6-nitroquinoxaline In J. Chem. Soc. According to the synthetic procedure described by Perkin I, 1975, 1229, 5-amino-6-nitroquinoxaline was prepared by reacting 6-nitroquinoxaline with hydroxylamine in an alkaline medium. The product was reacted analogously to Example 1) with sodium borohydride. The melting point of 1,2,2,3,4-tetrahydro-5-amino-6-nitroquinoxaline obtained as brown crystals (yield 11.5% of theory) was 213 ° C.

3) N, N'-dimethyl-1,2,3,4-tetrahydro-6-nitroquinoxaline

To a mixture of 1.08 g (0.006 mol) in J. Het. Chem., 10, 213 (1973), 1,2,3,4-tetrahydro-6-nitroquinoxaline and 1.5 g (0.005 mol) of paraformaldehyde in 300 ml of acetic acid were added at 25 ° C. 1.52 g (0.024 mol) of sodium cyanoborohydride. The solution was then allowed to stand for 24 hours at room temperature. The solution was then poured into 60 mL of 25% aqueous NaOH. The resulting mixture was extracted three times with methylene chloride. After drying and evaporation to dryness, 0.35 g (35% of theory) of N, N'-dimethyl-1,2,3,4-tetrahydro-6-nitroquinoxaline were obtained. The melting point of the product was 70 ° C.

4) 1- (N-methyl) -1,2,3,4-tetrahydro-6-nitroquinoxaline Step 1:

A mixture of 21.75 g (0.14 mol) of 2-fluoro-5-nitroaniline, 56 g (0.74 mol) of 2-methylaminoethanol and 1 g of copper (II) oxide was heated to 1.5 for one hour at 120 ° C. After cooling, the catalyst was filtered off and the solution was poured into ice water. The precipitate formed was filtered off with suction and dried in vacuo at + 70 ° C. The yield of 1- (N-methyl-N-O-hydroxyethyl) -2-amino-4-nitrobenzene was 25.5 g (96% of 9 100658 theoretical). The melting point of the product was 111-113 ° C.

Step 2: 5 g of the product of Step 1 was stirred over 15 minutes in 22 ml of phosphorus oxide trichloride at room temperature. The mixture was then heated in a water bath for 1 hour. After the excess phosphorus oxide trichloride was removed by distillation, 50 ml of distilled water was added to the residue. It was then extracted with diethyl ether. The orange oil obtained after evaporation to dryness of the ether phase was heated together with ethanol at reflux for 16 hours and then evaporated to dryness in vacuo. The obtained residue was dissolved in water, and a potassium carbonate solution was added thereto so that the mixture reacted alkaline. The precipitate formed was filtered off with suction and dried in vacuo at 60 ° C. There were thus obtained orange-red crystals of 1- (N-methyl) -1,2,3,4-tetrahydro-6-nitroquinoxaline. The UV spectrum of these crystals obtained using ethanol as a solvent showed a maximum at 441 nm, 350 nm and 290 nm.

Hair coloring tests

First, hair coloring creams were prepared having the following composition:

Fatty alcohol C12-C1 · 10 g

Fatty alcohol C12-C14 + 2 EO sulphate,

Na salt (28%) 25 g

Water 60 g

Direct dye 1 g

Ammonium sulphate 1 g Concentrated ammonia solution to give a pH of 9, 5

Water to give a total of 100 g.

The components were mixed successively. After the addition of the direct dye, the pH of the emulsion was adjusted to 9.5 with concentrated ammonia solution, followed by the addition of water to give a total of 100 g.

The color cream was applied to standardized, 90% gray, but in no particular pretreated, human hair extensions about 5 cm long and left to act for 30 minutes at 27 ° C. At the end of the coloring process, the hair was rinsed, washed with a conventional hair detergent, and finally dried.

The results of the staining experiments are shown in Table I.

Table I

Colored

Straight Color Hair Color 1,2,3,4-Tetrahydro-5-nitroquinoxaline red gray 1,2,3,4-tetrahydro-6-nitroquinoxaline copper 1,2,3,4-tetrahydro-7-nitro-2-oxoquinoxaline olive brown 1,2,3,4-Tetrahydro-2-methyl-6-nitroquinoxoline amber 1,2,3,4-tetrahydro-5-amino-6-nitroquinoxaline yellow N, N'-dimethyl-1, 2,3,4-Tetrahydro-6-nitroquinoxaline red orange 1- (N-methyl) -1,2,3,4-tetrahydro-6-nitroquinoxy reddish brown.

t

Claims (6)

100658 Hair dye substances containing direct dyes, characterized in that they contain as direct dyes one or more compounds of the formula (I) R 1 R 3 'R * in which one of the groups R 1 or R a is a nitro group and the other is hydrogen, halogen, amino group, mono - or a dialkylamino group having 1 to 4 carbon atoms in the alkyl groups, an alkyl or alkoxy group having in each case 1 to 4 carbon atoms, R * and R · * independently of one another denote hydrogen or an alkyl group having 1 to 4 carbon atoms, A is> CHRe or> C = O, the symbol R 6 denotes hydrogen or an alkyl group having 1 to 4 carbon atoms, and R 12 represents hydrogen or an alkyl group having 1 to 4 carbon atoms, or a salt thereof. Hair coloring agents according to Claim 1, characterized in that they contain 1,2,3,4-tetrahydro-5-nitroquinoxaline and / or 1,2,3,4-tetrahydro-6-nitroxene as direct dyes. . Hair colorants according to either of Claims 1 and 2, characterized in that they contain direct colorants of the formula (I) in an amount of 0.01 to 5% by weight, in particular 0.1 to 2% by weight, based on the total weight of the hair colorant. . Hair dyes according to one of Claims 1 to 3, characterized in that they contain, in addition to the compounds of the formula (I) 100658, other direct colorants and / or oxidative dye precursors. Hair colorants according to one of Claims 1 to 4, characterized in that these colorants are incorporated in a cosmetic carrier in the form of an ointment, emulsion, gel, shampoo or foam spray. Compounds of formula (I) according to claim 1, characterized in that they comprise the following substituent combinations (I) to (IV): R 1 R 2 R 3 R * R * AI: H NOa H CHa H CHa II: H NOa CHa CHa H CHa III: NHa NOa HHH CHa IV: H NOa HH CHa CHa. 100658